Polymerization catalyst compositions

ABSTRACT

This invention relates to a polymerization process comprising combining an olefin in the gas or slurry phase with a spray dried catalyst comprising an activator, a particulate filler and a metal catalyst compound.

FIELD OF THE INVENTION

[0001] This invention relates to spray dried olefin polymerizationcatalysts and their use in gas or slurry phase to produce polyolefins.

BACKGROUND OF THE INVENTION

[0002] The intense commercialization of metallocene polyolefin catalysts(metallocene being cyclopentadienyl based transition metal catalystcompounds) has led to widespread interest in the design ofnon-metallocene, homogeneous catalysts, particularly for use in theeconomical gas and slurry phase processes. This field is more than anacademic curiosity as new, non-metallocene catalysts in gas or slurryphase may provide an easier, more economical pathway to currentlyavailable products and may also provide product and processopportunities which are beyond the capability of metallocene catalystsin the gas or slurry phase.

[0003] New catalysts, however, are not automatically useable in the gasphase. Some catalysts are too active and foul the reactor. Othercatalysts cannot be supported and thus cannot be introduced into thereactor in such as way that fouling does not occur. Thus there is a needin the art for a method of providing catalysts to a gas phase or slurryphase reactor, particularly catalysts that are difficult or impossibleto support.

[0004] Schrock et al in U.S. Pat. No. 5, 889,128 discloses a process forthe living polymerization of olefins in solution using initiators havinga metal atom and a ligand having two group 15 atoms and a group 16 atomor three group 15 atoms. In particular, the solution phasepolymerization of ethylene using {[NON]ZrMe}[MeB(C₆F₅₎ ₃] or{[NON]ZrMe(PhNMe₂)]}[B(C₆F₅)₄] is disclosed in examples 9 and 10.

[0005] EP 893 454 A1 discloses unsupported transition metal amidecompounds used in combination with activators to polymerize olefins inthe solution phase.

[0006] Mitsui Chemicals, Inc. in EP 0 893 454 A1 discloses transitionmetal amides combined with activators to polymerize olefins.

[0007] EP 0 874 005 A1 discloses phenoxide compounds with an iminesubstituent for use as a polymerization catalyst.

[0008] EP 893 454 A1 discloses unsupported transition metal amidecompounds used in combination with activators to polymerize olefins inthe solution phase.

[0009] U.S. Ser. No. 09/312,878 filed May 17, 1999 discloses a gas orslurry phase polymerization process using a supported bisamide catalyst.

[0010] Japanese Abstract JP 10330416A appears to disclose transitionmetal amide catalysts in combination with Ziegler-Natta catalysts.Japanese Abstract JP 10330412A appears to disclose transition metalamide catalysts in combination with group 4 transition metalcyclopentadienyl catalysts.

[0011] Ethylenebis(salicylideneiminato)zirconium dichloride combinedwith methyl alumoxane deposited on a support and unsupported versionswere used to polymerize ethylene by Repo et al in Macromolecules 1997,30, 171-175.

[0012] U.S. Pat. No. 5,672,669, U.S. 674,795 and EP 0 668 295 B1disclose spray dried filled metallocene catalyst compositions for use ingas phase polymerizations.

SUMMARY OF THE INVENTION

[0013] This invention relates to a catalytic molecule, and a spray driedcatalyst system comprising a particulate filler, an activator, and ametal catalyst compound.

[0014] In one aspect the particulate filler may be any known particulatefiller including carbon black, talc; inorganic oxides such as silica;magnesium chloride, alumina, silica-alumina; polymeric materials such aspolyethylene, polypropylene, polystyrene, cross-linked polystyrene; andthe like.

[0015] Preferred activators include conventional-co-catalysts, alkylaluminum compounds (such as diethylaluminum chloride), alumoxanes,modified alumoxanes, non-coordinating anions, non-coordinating group 13metal or metalloid anions, boranes, borates and the like. It is withinthe scope of this invention to use alumoxane or modified alumoxane as anactivator, and/or to also use ionizing activators, neutral or ionic,such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron or atrisperfluorophenyl boron metalloid precursor which ionize the neutralmetallocene compound. Other useful compounds include triphenyl boron,triethyl boron, tri-n-butyl ammonium tetraethylborate, triaryl boraneand the like. Other useful compounds include aluminate salts as well.

[0016] Some of many metal catalyst compounds that may be used hereininclude a group 15 containing metal compound as described below and orphenoxide based catalysts as described below.

BRIEF DESCRIPTION OF THE DRAWINGS

[0017]FIG. 1 depicts the horizontally mixed reactor system used inComparative 9 and Examples 22 through 28.

DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention relates to a spray dried catalyst systemcomprising a particulate filler, an activator, and one or more metalcatalyst compounds. The metal catalyst compounds show the surprisingability to be immobilized with a filler, activated by an activator, andsurprising robustness and catalytic activity.

[0019] In a preferred embodiment herein the particulate filler is fumedsilica. Preferably the filler is Cabosil TS-610, available from CabotCorporation, which is a fumed silica with particles 7 to 30 nanometersin size that has been treated with dimethylsilyldichloride such that amajority of hydroxyl groups are capped. The spray dried particles aregenerally fed into the polymerization reactor as a mineral oil slurry.Solids concentrations in oil are about 10-15 weight %, preferably 11-14weight %. In some embodiments, the spray dried particles are <˜10micrometers in size from the lab-scale Buchi spray-dryer, while thescaled up rotary atomizers can create particles˜25 micrometers, comparedto conventional supported catalysts which are˜50 micrometers. In apreferred embodiment the particulate filler has an average particle sizeof 0.001 to 1 microns, preferably 0.001 to 0.1 microns.

[0020] In a preferred embodiment the metal catalyst compound comprisesone or more of the following catalysts:

[0021] Catalysts:

[0022] Preferred catalysts or catalysts systems that may be used hereininclude a group 15 containing metal compound and/or the phenoxidecatalysts as described below. Other catalysts that may be used incombination with the group 15 containing metal compound and/or thephenoxides include bulky ligand metallocene type catalysts with optionalactivator.

[0023] Once the catalysts described herein have been spray dried theymay be combined with other more conventional catalysts and introducedinto a reactor. For example a spray dried catalyst or mixture ofcatalysts can be combined with conventional type transition metalcatalysts (such as one or more Ziegler-Natta catalysts, vanadiumcatalysts and/or chromium catalysts) in a mineral oil and introducedinto a reactor in a slurry.

[0024] For more information on conventional type transition metalcatalysts please see Ziegler-Natta Catalysts and Polymerizations, JohnBoor, Academic Press, New York, 1979. Examples of conventional-typetransition metal catalysts are also discussed in U.S. Pat. Nos.4,115,639, 4,077,904, 4,482,687, 4,564,605, 4,721,763, 4,879,359,4,960,741, 4,302,565, 4,302,566, 5,317,036, 3,709,853, 3,709,954,3,231,550, 3,242,099, 4,077,904, 4,124,532, 4,302,565, 4,302,566,4,376,062, 4,379,758, 5,066,737, 5,763,723, 5,849,655, 5,852,144,5,854,164, 5,869,585, 3,487,112, 4,472,559, 4,182,814 and 4,689,437 andpublished EP-A2 0 416 815 A2 and EP-A1 0 420 436, and British PatentApplication 2,105,355.

[0025] For purposes of this invention cyclopentadienyl group is definedto include indenyls and fluorenyls.

[0026] Group 15 Containing Metal Compound:

[0027] The mixed catalyst composition of the present invention includesa Group 15 containing metal compound. The Group 15 containing compoundgenerally includes a Group 3 to 14 metal atom, preferably a Group 3 to7, more preferably a Group 4 to 6, and even more preferably a Group 4metal atom, bound to at least one leaving group and also bound to atleast two Group 15 atoms, at least one of which is also bound to a Group15 or 16 atom through another group.

[0028] In one preferred embodiment, at least one of the Group 15 atomsis also bound to a Group 15 or 16 atom through another group which maybe a C₁ to C₂₀ hydrocarbon group, a heteroatom containing group,silicon, germanium, tin, lead, or phosphorus, wherein the Group 15 or 16atom may also be bound to nothing or a hydrogen, a Group 14 atomcontaining group, a halogen, or a heteroatom containing group, andwherein each of the two Group 15 atoms are also bound to a cyclic groupand may optionally be bound to hydrogen, a halogen, a heteroatom or ahydrocarbyl group, or a heteroatom containing group.

[0029] In a preferred embodiment, the Group 15 containing metal compoundof the present invention may be represented by the formulae:

[0030] wherein

[0031] M is a Group 3 to 12 transition metal or a Group 13 or 14 maingroup metal, preferably a Group 4, 5, or 6 metal, and more preferably aGroup 4 metal, and most preferably zirconium, titanium or hafrlium,

[0032] each X is independently a leaving group, preferably, an anionicleaving group, and more preferably hydrogen, a hydrocarbyl group, aheteroatom or a halogen, and most preferably an alkyl.

[0033] y is 0 or 1 (when y is 0 group L′ is absent),

[0034] n is the oxidation state of M, preferably +3, +4, or +5, and morepreferably +4,

[0035] m is the formal charge of the YZL or the YZL′ ligand, preferably0, −1, −2 or −3, and more preferably −2,

[0036] L is a Group 15 or 16 element, preferably nitrogen,

[0037] L′ is a Group 15 or 16 element or Group 14 containing group,preferably carbon, silicon or germanium,

[0038] Y is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen,

[0039] Z is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen,

[0040] R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, aheteroatom containing group having up to twenty carbon atoms, silicon,germanium, tin, lead, halogen or phosphorus, preferably a C₂ to C₂₀alkyl, aryl or aralkyl group, more preferably a linear, branched orcyclic C₂ to C₂₀ alkyl group, most preferably a C₂ to C₆ hydrocarbongroup. R¹ and R² may also be interconnected to each other.

[0041] R³ is absent or a hydrocarbon group, hydrogen, a halogen, aheteroatom containing group, preferably a linear, cyclic or branchedalkyl group having 1 to 20 carbon atoms, more preferably R³ is absent,hydrogen or an alkyl group, and most preferably hydrogen

[0042] R⁴ and R⁵ are independently an alkyl group, an aryl group,substituted aryl group, a cyclic alkyl group, a substituted cyclic alkylgroup, a cyclic aralkyl group, a substituted cyclic aralkyl group ormultiple ring system, preferably having up to 20 carbon atoms, morepreferably between 3 and 10 carbon atoms, and even more preferably a C₁to C₂₀ hydrocarbon group, a C₁ to C₂₀ aryl group or a C₁ to C₂₀ aralkylgroup, or a heteroatom containing group, for example PR₃, where R is analkyl group,

[0043] R¹ and R² may be interconnected to each other, and/or R⁴ and R⁵may be interconnected to each other,

[0044] R⁶ and R⁷ are independently absent, or hydrogen, an alkyl group,halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclicor branched alkyl group having 1 to 20 carbon atoms, more preferablyabsent, and

[0045] R* is absent, or is hydrogen, a Group 14 atom containing group, ahalogen, ora heteroatom containing group.

[0046] By “formal charge of the YZL or YZL′ ligand”, it is meant thecharge of the entire ligand absent the metal and the leaving groups X.

[0047] By “R¹ and R² may also be interconnected” it is meant that R¹ andR² may be directly bound to each other or may be bound to each otherthrough other groups. By “R⁴ and R⁵ may also be interconnected” it ismeant that R⁴ and R⁵ may be directly bound to each other or may be boundto each other through other groups.

[0048] An alkyl group may be a linear, branched alkyl radicals, oralkenyl radicals, alkynyl radicals, cycloalkyl radicals or arylradicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxyradicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonylradicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof An aralkyl group is defined to be a substituted arylgroup.

[0049] In a preferred embodiment R⁴ and R⁵ are independently a grouprepresented by the following formula:

[0050] wherein

[0051] R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkylgroup, a halide, a heteroatom, a heteroatom containing group containingup to 40 carbon atoms, preferably a C₁ to C₂₀ linear or branched alkylgroup, preferably a methyl, ethyl, propyl or butyl group, any two Rgroups may form a cyclic group and/or a heterocyclic group. The cyclicgroups may be aromatic. In a preferred embodiment R⁹, R¹⁰ and R¹² areindependently a methyl, ethyl, propyl or butyl group (including allisomers), in a preferred embodiment R⁹, R¹⁰ and R¹² are methyl groups,and R⁸ and R¹¹ are hydrogen.

[0052] In a particularly preferred embodiment R⁴ and R⁵ are both a grouprepresented by the following formula:

[0053] In this embodiment, M is a Group 4 metal, preferably zirconium,titanium or hafnium, and even more preferably zirconium; each of L, Y,and Z is nitrogen; each of R¹ and R² is —CH₂—CH₂—; R³ is hydrogen; andR⁶ and R⁷ are absent.

[0054] In a particularly preferred embodiment the Group 15 containingmetal compound is represented by the formula:

[0055] In compound I, Ph equals phenyl.

[0056] The Group 15 containing metal compounds of the invention areprepared by methods known in the art, such as those disclosed in EP 0893 454 A1, U.S. Pat. No. 5,889,128 and the references cited in U.S.Pat. No. 5,889,128 which are all herein incorporated by reference. U.S.application Ser. No. 09/312,878, filed May 17, 1999, discloses a gas orslurry phase polymerization process using a supported bisamide catalyst,which is also incorporated herein by reference.

[0057] A preferred direct synthesis of these compounds comprisesreacting the neutral ligand, (see for example YZL or YZL′ of formula 1or 2) with M^(n)X_(n) (M is a Group 3 to 14 metal, n is the oxidationstate of M, each X is an anionic group, such as halide, in anon-coordinating or weakly coordinating solvent, such as ether, toluene,xylene, benzene, methylene chloride, and/or hexane or other solventhaving a boiling point above 60° C., at about 20 to about 150° C.(preferably 20 to 100° C.), preferably for 24 hours or more, thentreating the mixture with an excess (such as four or more equivalents)of an alkylating agent, such as methyl magnesium bromide in ether. Themagnesium salts are removed by filtration, and the metal complexisolated by standard techniques.

[0058] In one embodiment the Group 15 containing metal compound isprepared by a method comprising reacting a neutral ligand, (see forexample YZL or YZL′ of formula 1 or 2) with a compound represented bythe formula M^(n)X_(n) (where M is a Group 3 to 14 metal, n is theoxidation state of M, each X is an anionic leaving group) in anon-coordinating or weakly coordinating solvent, at about 20° C. orabove, preferably at about 20 to about 100° C., then treating themixture with an excess of an alkylating agent, then recovering the metalcomplex. In a preferred embodiment the solvent has a boiling point above60° C., such as toluene, xylene, benzene, and/or hexane. In anotherembodiment the solvent comprises ether and/or methylene chloride, eitherbeing preferable.

[0059] For additional information of Group 15 containing metalcompounds, please see Mitsui Chemicals, Inc. in EP 0 893 454 A1 whichdiscloses transition metal amides combined with activators to polymerizeolefins.

[0060] Phenoxide Catalysts:

[0061] Another group of catalysts that may be used in the process ofthis invention include one or more catalysts represented by thefollowing formulae:

[0062] wherein R¹ is hydrogen or a C₄ to C₁₀₀ group, preferably atertiary alkyl group, preferably a C₄ to C₂₀ alkyl group, preferably aC₄ to C₂₀ tertiary alkyl group, preferably a neutral C₄ to C₁₀₀ groupand may or may not also be bound to M, and at least one of R² to R⁵ is agroup containing a heteroatom, the rest of R² to R⁵ are independentlyhydrogen or a C₁ to C₁₀₀ group, preferably a C₄ to C₂₀ alkyl group(preferably butyl, isobutyl, pentyl hexyl, heptyl, isohexyl, octyl,isooctyl, decyl, nonyl, dodecyl ) and any of R² to R⁵ also may or maynot be bound to M, O is oxygen, M is a group 3 to group 10 transitionmetal or lanthanide metal, preferably a group 4 metal, preferably Ti, Zror Hf, n is the valence state of the metal M, preferably 2, 3, 4, or 5,Q is an alkyl, halogen, benzyl, amide, carboxylate, carbamate, thiolate,hydride or alkoxide group, or a bond to an R group containing aheteroatom which may be any of RI to R⁵ A heteroatom containing groupmay be any heteroatom or a heteroatom bound to carbon silica or anotherheteroatom. Preferred heteroatoms include boron, aluminum, silicon,nitrogen, phosphorus, arsenic, tin, lead, antimony, oxygen, selenium,tellurium. Particularly preferred heteroatoms include nitrogen, oxygen,phosphorus, and sulfur. Even more particularly preferred heteroatomsinclude oxygen and nitrogen. The heteroatom itself may be directly boundto the phenoxide ring or it may be bound to another atom or atoms thatare bound to the phenoxide ring. The heteroatom containing group maycontain one or more of the same or different heteroatoms. Preferredheteroatom groups include imines, amines, oxides, phosphines, ethers,ketenes, oxoazolines heterocyclics, oxazolines, thioethers, and thelike. Particularly preferred heteroatom groups include imines. Any twoadjacent R groups may form a ring structure, preferably a 5 or 6membered ring. Likewise the R groups may form multi-ring structures. Inone embodiment any two or more R groups do not form a 5 membered ring.

[0063] These phenoxide catalysts may be activated with activatorsincluding alkyl aluminum compounds (such as diethylaluminum chloride),alumoxanes, modified alumoxanes, non-coordinating anions,non-coordinating group 13 metal or metalliod anions, boranes, boratesand the like. For further information on activators please see theACTIVATOR section below.

[0064] This invention may also be practiced with the catalysts disclosedin EP 0 874 005 A1, which in incorporated by reference herein.

[0065] Activators:

[0066] The catalysts, preferably the group 15 metal compound and/or thephenoxide catalysts described herein, are preferably combined with oneor more activators to form olefin polymerization catalyst systems.Preferred activators include alkyl aluminum compounds (such asdiethylaluminum chloride), alumoxanes, modified alumoxanes,non-coordinating anions, non-coordinating group 13 metal or metalliodanions, boranes, borates and the like. It is within the scope of thisinvention to use alumoxane or modified alumoxane as an activator, and/orto also use ionizing activators, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron or a trisperfluorophenylboron metalloid precursor which ionize the neutral metallocene compound.Other useful compounds include triphenyl boron, triethyl boron,tri-n-butyl ammonium tetraethylborate, triaryl borane and the like.Other useful compounds include aluminate salts as well.

[0067] In one embodiment modified alumoxanes are combined with thecatalysts to form a catalyst system. In a preferred embodiment MMAO3A(modified methyl alumoxane in heptane, commercially available from AkzoChemicals, Inc. under the trade name Modified Methylalumoxane type 3A,covered under U.S. Pat. No. 5,041,584) is combined with the first andsecond metal compounds to form a catalyst system. MMAO-4 and MMAO-12 mayalso be used.

[0068] There are a variety of methods for preparing alumoxane andmodified alumoxanes, non-limiting examples of which are described inU.S. Pat. No. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529,5,041,584 5,693,838, 5,731,253, 5,041,584 and 5,731,451 and Europeanpublications EP-A-0 561 476, EP-B1-0 279 586 and EP-A-0 594-218, and PCTpublication WO 94/10180, all of which are herein fully incorporated byreference.

[0069] Ionizing compounds may contain an active proton, or some othercation associated with but not coordinated to or only looselycoordinated to the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-A-0 426 637, EP-A-500 944,EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157,5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,387,568, 5,384,299,5,502,124 and 5,643,847, all of which are herein fully incorporated byreference. Other activators include those described in PCT publicationWO 98/07515 such as tris (2, 2′, 2″- nonafluorobiphenyl)fluoroaluminate, which is fully incorporated herein by reference.Combinations of activators are also contemplated by the invention, forexample, alumoxanes and ionizing activators in combinations, see forexample, PCT publications WO 94/07928 and WO 95/14044 and U.S. Pat. Nos.5,153,157 and 5,453,410 all of which are herein fully incorporated byreference. Also, methods of activation such as using radiation and thelike are also contemplated as activators for the purposes of thisinvention.

[0070] When two different catalysts are used, the first and secondcatalyst compounds may be combined at molar ratios of 1:1000 to 1000:1,preferably 1:99 to 99:1, preferably 10:90 to 90:10, more preferably20:80 to 80:20, more preferably 30:70 to 70:30, more preferably 40:60 to60:40. The particular ratio chosen will depend on the end productdesired and/or the method of activation. One practical method todetermine which ratio is best to obtain the desired polymer is to startwith a 1:1 ratio, measure the desired property in the product producedand adjust the ratio accordingly.

[0071] In some embodiments one or more of the catalyst metal compoundsabove may be used in combination with a bulky ligand metallocenecompound (which is activated by the activators listed above.)

[0072] Bulky Ligand Metallocene-Type Compound:

[0073] Bulky ligand metallocene-type compound (hereinafer also referredto as metallocenes) may also be used in the practice of this invention.

[0074] Generally, bulky ligand metallocene-type compounds include halfand full sandwich compounds having one or more bulky ligands bonded toat least one metal atom. Typical bulky ligand metallocene-type compoundsare generally described as containing one or more bulky ligand(s) andone or more leaving group(s) bonded to at least one metal atom. In onepreferred embodiment, at least one bulky ligands is η-bonded to themetal atom, most preferably η⁵-bonded to the metal atom.

[0075] The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.These bulky ligands, preferably the ring(s) or ring system(s) aretypically composed of atoms selected from Groups 13 to 16 atoms of thePeriodic Table of Elements, preferably the atoms are selected from thegroup consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum or a combination thereof.Most preferably the ring(s) or ring system(s) are composed of carbonatoms such as but not limited to those cyclopentadienyl ligands orcyclopentadienyl-type ligand structures or other similar functioningligand structure such as a pentadiene, a cyclooctatetraendiyl or animide ligand. The metal atom is preferably selected from Groups 3through 15 and the lanthanide or actinide series of the Periodic Tableof Elements. Preferably the metal is a transition metal from Groups 4through 12, more preferably Groups 4, 5 and 6, and most preferably thetransition metal is from Group 4.

[0076] In one embodiment, the bulky ligand metallocene-type catalystcompounds are represented by the formula:

L^(A)L^(B)MQ_(n)  (III)

[0077] where M is a metal atom from the Periodic Table of the Elementsand may be a Group 3 to 12 metal or from the lanthanide or actinideseries of the Periodic Table of Elements, preferably M is a Group 4, 5or 6 transition metal, more preferably M is a Group 4 transition metal,even more preferably M is zirconium, haffiium or titanium. The bulkyligands, L^(A) and L^(B), are open, acyclic or fused ring(s) or ringsystem(s) and are any ancillary ligand system, including unsubstitutedor substituted, cyclopentadienyl ligands or cyclopentadienyl-typeligands, heteroatom substituted and/or heteroatom containingcyclopentadienyl-type ligands. Non-limiting examples of bulky ligandsinclude cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands,indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of η-bonding to M, preferablyη³-bonding to M and most preferably η⁵-bonding. In yet anotherembodiment, the atomic molecular weight (MW) of L^(A) or L^(B) exceeds60 a.m.u., preferably greater than 65 a.m.u. In another embodiment,L^(A) and L^(B) may comprise one or more heteroatoms, for example,nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other LA and LB bulky ligands include but are notlimited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof formula (III) only one of either L^(A) or L^(B) is present.

[0078] Independently, each L^(A) and L^(B) may be unsubstituted orsubstituted with a combination of substituent groups R. Non-limitingexamples of substituent groups R include one or more from the groupselected from hydrogen, or linear, branched alkyl radicals, or alkenylradicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acylradicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. In a preferred embodiment, substituent groups Rhave up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, thatcan also be substituted with halogens or heteroatoms or the like.Non-limiting examples of alkyl substituents R include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenylgroups and the like, including all their isomers, for example tertiarybutyl, isopropyl, and the like. Other hydrocarbyl radicals includefluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl,chlorobenzyl and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

[0079] Other ligands may be bonded to the metal M, such as at least oneleaving group Q. In one embodiment, Q is a monoanionic labile ligandhaving a sigma-bond to M. Depending on the oxidation state of the metal,the value for n is 0, 1 or 2 such that formula (III) above represents aneutral bulky ligand metallocene-type catalyst compound.

[0080] Non-limiting examples of Q ligands include weak bases such asamines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicalshaving from 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike.

[0081] The two L groups may be bridged together by group A as definedbelow.

[0082] In one embodiment, the bulky ligand metallocene-type catalystcompounds of the invention include those of formula (III) where L^(A)and L^(B) are bridged to each other by at least one bridging group, A,such that the formula is represented by

L^(A)AL^(B) MQ_(n)  (IV)

[0083] These bridged compounds represented by formula (IV) are known asbridged, bulky ligand metallocene-type catalyst compounds. L^(A), L^(B),M, Q and n are as defined above. Non-limiting examples of bridging groupA include bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, silicon, aluminum, boron,germanium and tin atom or a combination thereof. Preferably bridginggroup A contains a carbon, silicon or germanium atom, most preferably Acontains at least one silicon atom or at least one carbon atom. Thebridging group A may also contain substituent groups R as defined aboveincluding halogens and iron. Non-limiting examples of bridging group Amay be represented by R′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ isindependently, a radical group which is hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen, or halogen or two or more R′ may be joined toform a ring or ring system. In one embodiment, the bridged, bulky ligandmetallocene-type catalyst compounds of formula (IV) have two or morebridging groups A (EP 664 301 B1).

[0084] In one embodiment, the bulky ligand metallocene-type catalystcompounds are those where the R substituents on the bulky ligands L^(A)and L^(B) of formulas (III) and (IV) are substituted with the same ordifferent number of substituents on each of the bulky ligands. Inanother embodiment, the bulky ligands L^(A) and L^(B) of formulas (III)and (IV) are different from each other.

[0085] Other bulky ligand metallocene-type catalyst compounds andcatalyst systems useful in the invention may include those described inU.S. Pat. Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022,5,276,208, 5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401,5,723,398, 5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158,5,900,517 and 5,939,503 and PCT publications WO 93/08221, WO 93/08199,WO 95/07140, WO 98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO99/02540 and WO 99/14221 and European publications EP-A-0 578 838,EP-A-0 638 595, EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834,EP-B1-0 632 819, EP-B1-0 748 821 and EP-B1-0 757 996, all of which areherein fully incorporated by reference.

[0086] In one embodiment, bulky ligand metallocene-type catalystscompounds useful in the invention include bridged heteroatom, mono-bulkyligand metallocene-type compounds. These types of catalysts and catalystsystems are described in, for example, PCT publication WO 92/00333, WO94/07928, WO 91/04257, WO 94/03506, WO96/00244, WO 97/15602 and WO99/20637 and U.S. Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401,5,227,440 and 5,264,405 and European publication EP-A-0 420 436, all ofwhich are herein fully incorporated by reference.

[0087] In this embodiment, the bulky ligand metallocene-type catalystcompound is represented by the formula:

L^(C)AJMQ_(n)  (V)

[0088] where M is a Group 3 to 16 metal atom or a metal selected fromthe Group of actinides and lanthanides of the Periodic Table ofElements, preferably M is a Group 4 to 12 transition metal, and morepreferably M is a Group 4, 5 or 6 transition metal, and most preferablyM is a Group 4 transition metal in any oxidation state, especiallytitanium; L^(C) is a substituted or unsubstituted bulky ligand bonded toM; J is bonded to M; A is bonded to M and J; J is a heteroatom ancillaryligand; and A is a bridging group; Q is a univalent anionic ligand; andn is the integer 0,1 or 2. In formula (V) above, L^(C), A and J form afused ring system. In an embodiment, L^(C) of formula (V) is as definedabove for L^(A), A, M and Q of formula (V) are as defined above informula (III).

[0089] In formula (V) J is a heteroatom containing ligand in which J isan element with a coordination number of three from Group 15 or anelement with a coordination number of two from Group 16 of the PeriodicTable of Elements. Preferably J contains a nitrogen, phosphorus, oxygenor sulfur atom with nitrogen being most preferred.

[0090] In an embodiment of the invention, the bulky ligandmetallocene-type catalyst compounds are heterocyclic ligand complexeswhere the bulky ligands, the ring(s) or ring system(s), include one ormore heteroatoms or a combination thereof. Non-limiting examples ofheteroatoms include a Group 13 to 16 element, preferably nitrogen,boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examplesof these bulky ligand metallocene-type catalyst compounds are describedin WO 96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874005 and U.S. Pat. Nos. 5,637,660, 5,539,124, 5,554,775, 5,756,611,5,233,049, 5,744,417, and 5,856,258 all of which are herein incorporatedby reference.

[0091] In one embodiment, the bulky ligand metallocene-type catalystcompounds are those complexes known as transition metal catalysts basedon bidentate ligands containing pyridine or quinoline moieties, such asthose described in U.S. application Ser. No. 09/103,620 filed Jun. 23,1998, which is herein incorporated by reference. In another embodiment,the bulky ligand metallocene-type catalyst compounds are those describedin PCT publications WO 99/01481 and WO 98/42664, which are fullyincorporated herein by reference.

[0092] In a preferred embodiment, the bulky ligand type metallocene-typecatalyst compound is a complex of a metal, preferably a transitionmetal, a bulky ligand, preferably a substituted or unsubstitutedpi-bonded ligand, and one or more heteroallyl moieties, such as thosedescribed in U.S. Pat. Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057,all of which are herein fully incorporated by reference.

[0093] In a particularly preferred embodiment, the other metal compoundor second metal compound is the bulky ligand metallocene-type catalystcompound is represented by the formula:

L^(D)MQ₂(YZ)X_(n)  (VI)

[0094] where M is a Group 3 to 16 metal, preferably a Group 4 to 12transition metal, and most preferably a Group 4, 5 or 6 transitionmetal; LD is a bulky ligand that is bonded to M; each Q is independentlybonded to M and Q₂(YZ) forms a ligand, preferably a unichargedpolydentate ligand; A or Q is a univalent anionic ligand also bonded toM; X is a univalent anionic group when n is 2 or X is a divalent anionicgroup when n is 1; n is 1 or 2.

[0095] In formula (VI), L and M are as defined above for formula (III).Q is as defined above for formula (III), preferably Q is selected fromthe group consisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Zis selected from the group consisting of —OR, —NR₂, —CR₃, SR, —SiR₃,—PR₂, —H, and substituted or unsubstituted aryl groups, with the provisothat when Q is —NR— then Z is selected from one of the group consistingof —OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

[0096] Spray-Drying:

[0097] The metal compounds and/or the activators are then preferablycombined with a particulate filler material and then spray dried,preferably to form a free flowing powder.

[0098] Spray drying may be by any means known in the art. Please see EPA0 668 295 B1, U.S. Pat. No. 5,674,795 and U.S. Pat. No. 5,672,669 whichparticularly describe spray drying of supported catalysts. In generalone may spray dry the catalysts by placing the metal catalyst compoundand the activator in solution, allowing them to react, then adding afiller material such as silica or Cabosil™, then forcing the solution athigh pressures through a nozel. The catalyst may be sprayed onto asurface or sprayed such that the droplets dry in midair. The methodgenerally employed is to disperse the silica in toluene, stir in theactivator solution, and then stir in the catalyst precursor solution.Typical slurry concentrations are about 5-8 wt %. This formulation maysit as a slurry for as long as 30 minutes with mild stirring or manualshaking to keep it as a suspension before spray-drying. In one preferredembodiment, the makeup of the dried material is about 40-50 wt %activator, (preferably alumoxane), 50-60 SiO₂ and about˜2 wt % metalcatalyst compound.

[0099] For simple metal catalyst compound mixtures, the two or moremetal catalyst compounds can be added together in the desired ratio inthe last step. In aonther embodiment, more complex procedures arepossible, such as addition of a first metal catalyst compound to theactivator/filler mixture for a specified reaction time t, followed bythe addition of the second metal catalyst compound solution, mixed foranother specified time x, after which the mixture is cosprayed. Lastly,another additive, such as 1-hexene in about 10 vol % can be present inthe activator/filler mixture prior to the addition of the first metalcatalyst compound.

[0100] In another embodiment a bulky ligand metallocene type compoundand optional activator can be combined with the spray dried catalysts ofthis invention and then introduced into a reactor.

[0101] In another embodiment binders are added to the mix. These can beadded as a means of improving the particle morphology, i.e. narrowingthe particle size distribution, lower porosity of the particles andallowing for a reduced quantity of alumoxane, which is acting as the‘binder’.

[0102] Polymerization Process of the Invention:

[0103] The catalysts and catalyst systems described above are suitablefor use in the polymerization process of the invention. Thepolymerization process of the invention includes a solution, gas orslurry process or a combination thereof, most preferably a gas or slurryphase process.

[0104] In an embodiment, this invention is directed toward the slurry orgas phase polymerization or copolymerization reactions involving thepolymerization of one or more monomers having from 2 to 30 carbon atoms,preferably 2-12 carbon atoms, and more preferably 2 to 8 carbon atoms.The invention is particularly well suited to the copolymerizationreactions involving the polymerization of one or more olefin monomers ofethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1,octene-1, decene-1, 3-methyl-pentene-1, 3,5,5-trimethyl-hexene-l andcyclic olefins or a combination thereof. Other monomers can includevinyl monomers, diolefins such as dienes, polyenes, norbornene,norbornadiene monomers. Preferably a copolymer of ethylene is produced,where the comonomer is at least one alpha-olefin having from 4 to 15carbon atoms, preferably from 4 to 12 carbon atoms, more preferably from4 to 8 carbon atoms and most preferably from 4 to 7 carbon atoms. In analternate embodiment, the geminally disubstituted olefins disclosed inWO 98/37109 may be polymerized or copolymerized using the inventionherein described.

[0105] In another embodiment ethylene or propylene is polymerized withat least two different comonomers to form a terpolymer. The preferredcomonomers are a combination of alpha-olefin monomers having 4 to 10carbon atoms, more preferably 4 to 8 carbon atoms, optionally with atleast one diene monomer. The preferred terpolymers include thecombinations such as ethylene/butene-1/hexene-1,ethylene/propylene/butene-1, propylene/ethylene/hexene-1,ethylene/propylene/norbornene and the like.

[0106] In a particularly preferred embodiment the process of theinvention relates to the polymerization of ethylene and at least onecomonomer having from 4 to 8 carbon atoms, preferably 4 to 7 carbonatoms. Particularly, the comonomers are butene-1, 4-methyl-pentene-1,hexene-1 and octene-1, the most preferred being hexene-1 and/orbutene-1.

[0107] Typically in a gas phase polymerization process a continuouscycle is employed where in one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228 all of which are fully incorporated herein byreference.)

[0108] The reactor pressure in a gas phase process may vary from about10 psig (69 kPa) to about 500 psig (3448 kPa), preferably in the rangeof from about 100 psig (690 kPa) to about 400 psig (2759 kPa),preferably in the range of from about 200 psig (1379 kPa) to about 400psig (2759 kPa), more preferably in the range of from about 250 psig(1724 kPa) to about 350 psig (2414 kPa).

[0109] The reactor temperature in the gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about115° C., more preferably in the range of from about 70° C. to 110° C.,and most preferably in the range of from about 70° C. to about 95° C.

[0110] The productivity of the catalyst or catalyst system is influencedby the main monomer partial pressure. The preferred mole percent of themain monomer, ethylene or propylene, preferably ethylene, is from about25 to 90 mole percent and the monomer partial pressure is in the rangeof from about 75 psia (517 kPa) to about 300 psia (2069 kPa), which aretypical conditions in a gas phase polymerization process.

[0111] In a preferred embodiment, the reactor utilized in the presentinvention and the process of the invention produce greater than 500 lbsof polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr)or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr),more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even morepreferably greater than 25,000 lbs/hr (11,300 Kg/hr), still morepreferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even morepreferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferablygreater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr(45,500 Kg/hr).

[0112] Other gas phase processes contemplated by the process of theinvention include those described in U.S. Pat. Nos. 5,627,242, 5,665,818and 5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202and EP-B-634 421 all of which are herein fully incorporated byreference.

[0113] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres and even greater andtemperatures in the range of 0° C. to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which ethylene and comonomersand often hydrogen along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[0114] In one embodiment, a preferred polymerization technique of theinvention is referred to as a particle form polymerization, or a slurryprocess where the temperature is kept below the temperature at which thepolymer goes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 185° F. (85° C.) toabout 230° F. (110° C.). Two preferred polymerization methods for theslurry process are those employing a loop reactor and those utilizing aplurality of stirred reactors in series, parallel, or combinationsthereof. Non-limiting examples of slurry processes include continuousloop or stirred tank processes. Also, other examples of slurry processesare described in U.S. Pat. No. 4,613,484, which is herein fullyincorporated by reference.

[0115] In another embodiment, the slurry process is carried outcontinuously in a loop reactor. The catalyst as a slurry in isobutane oras a dry free flowing powder is injected regularly to the reactor loop,which is itself filled with circulating slurry of growing polymerparticles in a diluent of isobutane containing monomer and comonomer.Hydrogen, optionally, may be added as a molecular weight control. Thereactor is maintained at pressure of about 525 psig to 625 psig (3620kPa to 4309 kPa) and at a temperature in the range of about 140° F. toabout 220° F. (about 60° C. to about 104° C.) depending on the desiredpolymer density. Reaction heat is removed through the loop wall sincemuch of the reactor is in the form of a double-jacketed pipe. The slurryis allowed to exit the reactor at regular intervals or continuously to aheated low pressure flash vessel, rotary dryer and a nitrogen purgecolumn in sequence for removal of the isobutane diluent and allunreacted monomer and comonomers. The resulting hydrocarbon free powderis then compounded for use in various applications.

[0116] In an embodiment the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

[0117] In another embodiment in the slurry process of the invention thetotal reactor pressure is in the range of from 400 psig (2758 kPa) to800 psig (5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig(4827 kPa), more preferably 500 psig (3448 kPa) to about 650 psig (4482kPa), most preferably from about 525 psig (3620 kPa) to 625 psig (4309kPa).

[0118] In yet another embodiment in the slurry process of the inventionthe concentration of ethylene in the reactor liquid medium is in therange of from about 1 to 10 weight percent, preferably from about 2 toabout 7 weight percent, more preferably from about 2.5 to about 6 weightpercent, most preferably from about 3 to about 6 weight percent.

[0119] A preferred process of the invention is where the process,preferably a slurry or gas phase process is operated in the absence ofor essentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This preferredprocess is described in PCT publication WO 96/08520 and U.S. Pat. No.5,712,352, which are herein fully incorporated by reference.

[0120] In another preferred embodiment the one or all of the catalystsare combined with up to 10 weight % of a metal stearate, (preferably aaluminum stearate, more preferably aluminum distearate) based upon theweight of the catalyst, any support and the stearate, preferably 2 to 3weight %. In an alternate embodiment a solution of the metal stearate isfed into the reactor. In another embodiment the metal stearate is mixedwith the catalyst and fed into the reactor separately. These agents maybe mixed with the catalyst or may be fed into the reactor in a solutionwith or without the catalyst system or its components.

[0121] In a preferred embodiment, the polyolefin recovered typically hasa melt index as measured by ASTM D-1238, Condition E, at 190° C. of 3000g/10 min or less. In a preferred embodiment the polyolefin is ethylenehomopolymer or copolymer. IN a preferred embodiment for certainapplications, such as films, molded article and the like a melt index of100 g/10 min or less is preferred. For some films and molded article amelt index of 10 g/10 min is preferred. In a preferred embodiment thepolymer produced has a molecular weight of 200,000 Daltons or more.

[0122] In a preferred embodiment the catalyst system described above isused to make a polyethylene having a density of between 0.88 and 0.970g/cm³ (as measured by ASTM 2839), a melt index of 1.0 or less g/10 minor less (as measured by ASTM D-1238, Condition E, at 190° C.).Polyethylene having a melt index of between 0.01 to 10 dg/min ispreferably produced. In some embodiments, a density of 0.915 to 0.940g/cm³ would be preferred, in other embodiments densities of 0.930 to0.960 g/cm³ are preferred.

[0123] The polyolefins then can be made into films, molded articles,sheets, wire and cable coating and the like. The films may be formed byany of the conventional technique known in the art including extrusion,co-extrusion, lamination, blowing and casting. The film may be obtainedby the flat film or tubular process which may be followed by orientationin an uniaxial direction or in two mutually perpendicular directions inthe plane of the film to the same or different extents. Orientation maybe to the same extent in both directions or may be to different extents.Particularly preferred methods to form the polymers into films includeextrusion or coextrusion on a blown or cast film line.

[0124] The films produced may further contain additives such as slip,antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers,antistats, polymer processing aids, neutralizers, lubricants,surfactants, pigments, dyes and nucleating agents. Preferred additivesinclude silicon dioxide, synthetic silica, titanium dioxide,polydimethylsiloxane, calcium carbonate, metal stearates, calciumstearate, zinc stearate, talc, BaSO₄, diatomaceous earth, wax, carbonblack, flame retarding additives, low molecular weight resins,hydrocarbon resins, glass beads and the like. The additives may bepresent in the typically effective amounts well known in the art, suchas 0.001 weight % to 10 weight %.

[0125] This invention further relates to a library of a plurality ofmetal compounds represented by the formula above. These libraries maythen be used for the simultaneous parallel screening of catalysts bycombining the library with one or more olefins, preferably in order todetermine the relative capabilities of the different compounds.

EXAMPLES

[0126] Mn and Mw were measured by gel permeation chromatography on awaters 150° C. GPC instrument equipped with differential refractionindex detectors. The GPC columns were calibrated by running a series ofnarrow polystyrene standards and the molecular weights were calculatedusing Mark Houwink coefficients for the polymer is question.

[0127] Density was measured according to ASTM D 1505.

[0128] Melt Index (MI) I₂ and I₂₁ were measured according to ASTMD-1238, Condition E, at 190° C.

[0129] Melt Index Ratio (MIR) is the ratio of I₂₁ over I₂ as determinedby ASTM D-1238.

[0130] Weight % comonomer was measured by proton NMR.

MWD=Mw/Mn

[0131] A={[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂

[0132] B=[(2-Me-naphthyl)NCH₂CH₂]₂NH]ZrBz₂

[0133] C={[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}HfBz₂

Example 1

[0134] Preparation of [(2,4,6-Me₃C₆H₂)NHCH₂CH₂]NH Ligand

[0135] A 2 L one-armed Schlenk flask was charged with a magnetic stirbar, diethylenetriamine (23.450 g, 0.227 mol), 2-bromomesitylene (90.51g, 0.455 mol), tris(dibenzylideneacetone)dipalladium (1.041 g, 1.14mol), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (racemicBINAP) (2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol),and toluene (800 mL) under dry, oxygen-free nitrogen. The reactionmixture was stirred and heated to 100 C. After 18 h the reaction wascomplete, as judged by proton NMR spectroscopy. All remainingmanipulations can be performed in air. All solvent was removed undervacuum and the residues dissolved in diethyl ether (1 L). The ether waswashed with water (3×250 mL) followed by saturated aqueous NaCl (180 gin 500 mL) and dried over magnesium sulfate (30 g). Removal of the etherin vacuo yielded a red oil which was dried at 70 C for 12 h under vacuum(yield: 71.10 g, 92%). ¹H NMR (C₆D₆) δ6.83 (s, 4), 3.39 (br s, 2), 2.86(t, 4), 2.49 (t, 4), 2.27 (s, 12), 2.21 (s, 6), 0.68 (br s, 1).

Example 2

[0136] (Preparation of Catalyst A)

[0137] Preparation of {[(2,4,6-Me₃C₆H₂)NCH₂CH₂]NH}Zr(CH₂Ph)₂

[0138] A 500 mL round bottom flask was charged with a magnetic stir bar,tetrabenzyl zirconium (Boulder Scientific) (41.729 g, 91.56 mmol), and300 mL of toluene under dry, oxygen-free nitrogen. Solid HN3 ligand(example 1) (32.773 g, 96.52 mmol) was added with stirring over 1 minute(the desired compound precipitates). The volume of the slurry wasreduced to 100 mL and 300 mL of pentane added with stirring. The solidyellow-orange product was collected by filtration and dried under vacuum(44.811 g, 80% yield). ¹H NMR (C₆D₆) δ7.22-6.81 (m, 12), 5.90 (d, 2),3.38 (m, 2), 3.11 (m, 2), 3.01 (m, 1), 2.49 (m, 4), 2.43 (s, 6), 2.41(s, 6), 2.18 (s, 6), 1.89 (s, 2), 0.96 (s, 2).

Example 3

[0139] (Preparation of Catalyst C)

[0140] Preparation of {[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}Hf(CH₂Ph)₂)

[0141] A 250 mL round bottom flask was charged with a magnetic stir bar,tetrabenzyl haffiium (4.063 g, 7.482 mmol), and 150 mL of toluene underdry, oxygen-free nitrogen. Solid HN3 ligand (Example 1) (2.545 g, 7.495mmol) was added with stirring over 1 minute (the desired compoundprecipitates). The volume of the slurry was reduced to 30 mL and 120 mLof pentane added with stirring. The solid pale yellow product wascollected by filtration and dried under vacuum (4.562 g, 87% yield). ¹HNMR (C₆D₆) δ7.21-6.79 (m, 12), 6.16 (d, 2), 3.39 (m, 2), 3.14 (m, 2),2.65 (s, 6), 2.40 (s, 6), 2.35 (m, 2), 2.23 (m, 2), 2.19 (s, 6) 1.60 (s,2), 1.26 (s, 2), NH obscured.

Example 4

[0142] Preparation of [(2-methylnaphthyls)NHCH₂C₂]₂NH Ligand

[0143] A 1 L one-arned Schlenk flask was charged with a magnetic stirbar, diethylenetriamine (6.026 g, 58.41 mmol),2-bromo-2-methylnaphthylene (25.829 g, 116.8 mmol),tris(dibenzylidene-acetone)dipalladium (0.268 g, 0.292 mmol),racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (racemic BINAP)(0.547 g, 0.878 mmol), sodium tert-butoxide (16.90 g, 175.8 mmol), andtoluene (400 mL) under dry, oxygen-free nitrogen. The reaction mixturewas stirred and heated to 100 C. After 18 h the reaction was complete,as judged by proton NMR spectroscopy. All remaining manipulations can beperformed in air. All solvent was removed under vacuum and the residuesdissolved in diethyl ether (500 mL). The ether was washed with water(3×100 mL) followed by saturated aqueous NaCl (90 g in 250 mL) and driedover magnesium sulfate (15 g). Removal of the ether in vacuo yielded ared oil which was dried at 70 C for 12 h under vacuum (yield: 19.10 g,85%). ¹HNMR(C₆D₆) δ8.32 (d, 2), 7.71 (d, 2), 7.40-7.18 (m, 8), 3.91 (t,2), 2.99 (dt, 4), 2.41 (dt, 4), 2.30 (s, 6), 0.69 (pentet, 1).

Example 5

[0144] (Preparation of Catalyst C)

[0145] Preparation of {[(2-methylnaphthyl)NCH₂CH₂]₂NH}Zr(CH₂Ph)₂

[0146] A 500 mL round bottom flask was charged with a magnetic stir bar,tetrabenzyl zirconium (Boulder Scientific) (3.000 g, 6.582 mmol), and300 mL of toluene under dry, oxygen-free nitrogen. A solution HN3-2ligand (Example 4) (65 mL, 0.102 M, -6.63 mmol) was added with stirringover 1 minute (the desired compound precipitates). The volume of theslurry was reduced to 40 mL and 150 mL of pentane added with stirring.The solid yellow-orange product was collected by filtration and driedunder vacuum (3.060 g, 71% yield). The product is a mixture of fourisomers resulting from the orientation of the 2-methylnaphthyl groups.¹H NMR (C₆D₆) δ8.50 (d), 8.39 (d), 8.35 (d), 7.70 (d), 7.66-6.70 (m),6.53 (t), 6.22 (t), 5.63 (m), 5.18 (d), 4.70 (d), 3.62 (m), 3.50 (m),3.30-3.11 (m), 2.68 (m), 2.60 (s), 2.55 (m), 2.52 (s), 2.50 (s), 2.10(s), 1.61 (s), 1.29 (AB quartet), 1.03 (s), 1.01 (s), 1.00 (AB quartet),other resonances obscured.

Example 6

[0147] Synthesis of [ortho-3,5-di-t-Bu-(C₆H₂)(OH)CH═NCHMe₂].3,5-Di-t-butylsalicylaldehyde (3.00 g) was added to 10 mL ofiso-propylamine. The solution rapidly turned bright yellow. Afterstirring at ambient temperature for 3 hours, volatiles were removedunder vacuum to yield a bright yellow, crystalline solid (97% yield).

Example 7

[0148] (Preparation of Catalyst D)

[0149] Synthesis of {[ortho-3,5-di-t-Bu-(C₆H₂)(O)CH═NCHMe₂]₂Zr(CH₂Ph)₂.

[0150] A solution of N-iso-Pr-3,5-di-t-butylsalicylimine (605 mg, 2.2mmol) in 5 mL toluene was slowly added to a solution of Zr(CH₂Ph)₄ (500mg, 1.1 mmol) in 50 mL toluene. The resulting dark yellow solution wasstirred for 30 min. Solvent was removed in vacuo to yield areddish-brown solid. ¹H NMR (C₆D₆) δ8.07 (s, HC═N, 1H), 7.77 (d, J=2.4Hz, salicylimine), 7.1-6.95 (m, 5H, aryl), 6.73 (t, J=7.2 Hz, 1H,benzyl), 4.17 (septet, J=6.6 Hz, 1H, CHMe₂), 2.76 (AB, J=10.2 Hz, 2H,ZrCH₂Ph), 1.78 (s, 9H, t-Bu), 1.29 (s, 9H, t-Bu), 0.76 (d, J=6.6 Hz, 3H,NCHMe_(A)Me_(B)), 0.52 (d, J=6.6 Hz, 3H, NCHMe_(A)Me_(B)).

[0151] Catalyst 1. Spray-Drying of {[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBZ₂

[0152] To 110 mls of toluene was added to 5.0 gms of Cabosil TS-610,dehydrated under vacuum above 100° C. To this slurry was added asolution of methylalumoxane (26 mls of 20 wt % MAO in toluene). Acatalyst precursor solution of 0.075 gms[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH]ZrBz₂ in about 20 mls toluene was added tothe slurry, and stirred/swirled for about 30 minutes. This mixture wasspray dried in a Buchi Series 190 Mini Spray Dryer, contained in aninert atmosphere drybox. The following conditions were employed: a 0.7mm diameter spray nozzle cap, a 0.5 mm mixing needle, nitrogen gasflowing at 16.7 L/min for spray-flow, an aspirator setting at 20, 120°C. inlet temperature, 80 to 90° C. outlet temperature, and 0.6 L/hrcatalyst mixture feed. The solids collected totaled 6.55 gins (68%). ICPindicated 0.13 wt % Zr and an Al:Zr ratio of 536:1.

[0153] Catalyst 2. Spray-Drying of {[(2-Me-Naphthyl)NCH₂CH₂]₂NH}ZrBz₂

[0154] To 110 mls of toluene was added to 5.0 gms of Cabosil TS-610,dehydrated under vacuum above 100° C. To this slurry was added asolution of methylalumoxane (26 mls of 20 wt % MAO in toluene). Acatalyst precursor solution of 0.083 gms[(2-Me-naphthyl)NCH₂CH₂]₂NH]ZrBz₂ in about 20 mls toluene was added tothe slurry, and stirred/swirled for about 30 minutes. This mixture wasspray dried as above. The solids collected totaled 5.77 gms (59%). ICPindicated 0.15 wt % Zr and an Al:Zr ratio of 458:1.

[0155] Catalyst 3. Spray-Drying of {[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂

[0156] To 110 mls of toluene was added to 4.0 gms of Cabosil TS-610,dehydrated under vacuum above 100° C. To this slurry was added asolution of methylalumoxane (26 mls of 20 wt % MAO in toluene). Acatalyst precursor solution of 0.20 gms[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH]ZrBz₂ in about 20 mls toluene was added tothe slurry, and stirred/swirled for about 30 minutes. This mixture wasspray dried as above. The solids collected totaled 5.18 gms (58%). ICPindicated 0.36 wt % Zr and an Al:Zr ratio of 196:1.

[0157] Catalyst 4. Spray-Drying of {[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}HfBz₂

[0158] To 140 mls of toluene was added 4.6 gms of Cabosil TS-610,dehydrated under vacuum above 100° C. To this slurry was added asolution of methylalumoxane (20.8 mls of 20 wt % MAO in toluene). Acatalyst precursor solution of 0.229 gms[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH]HfBz₂ in about 20 mls toluene was added tothe slurry, and stirred/swirled for about 30 minutes. This mixture wasspray dried as above.

[0159] Catalyst 5. Spray-Drying of {[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂

[0160] To 280 mls of toluene was added to 12.4 gms of Cabosil TS-610,dehydrated under vacuum above 100° C. To this slurry was added asolution of methylalumoxane (57 mls of 20 wt % MAO in toluene). Acatalyst precursor solution of 0.55 gms[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH]ZrBz₂ in about 20 mls toluene was added tothe slurry, and stirred/swirled for about 30 minutes. This mixture wasspray dried as above. The solids collected totaled 13 gms (56%). ICPindicated 0.38 wt % Zr and an Al:Zr ratio of 152:1.

[0161] Catalyst 6. Spray-Drying of {[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}HfBz₂

[0162] To 125 mls of toluene was added 6.0 gms of Cabosil TS-610,dehydrated under vacuum above 100° C. To this slurry was added asolution of methylalumoxane (27 mls of 20 wt % MAO in toluene). Acatalyst precursor solution of 0.30 gms[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH]HfBz₂ in about 20 mls toluene was added tothe slurry, and stirred/swirled for about 30 minutes. This mixture wasspray dried as above. The solids collected totaled 7.0 gms (63%). ICPindicated 0.72 wt % Hf and an Al:Hf ratio of 120: 1.

[0163] Catalyst 7. Spray-Drying of{[ortho-3,5-di-t-Bu-(C₆H₂)(O)CH═NCHMe₂]₂}Zr(CH₂Ph)₂

[0164] To 75 mls of toluene was added 2.6 gms of Cabosil TS-610,dehydrated under vacuum above 100° C. To this slurry was added asolution of methylalumoxane (12.4 mls of 20 wt % MAO in toluene). Acatalyst precursor solution of 0.168 gms{[ortho-3,5-di-t-Bu-(C₆H₂)(O)CH═NCHMe₂]₂}Zr(CH₂Ph)₂ in about 20 mlstoluene was added to the slurry, and stirred/swirled for about 30minutes. This mixture was spray dried as above.

[0165] Catalyst 8. Spray-Drying of 1:1{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂ and (n-C₃H₇-C₅H₄)(Me₅C)ZrCl₂

[0166] To 110 mls of toluene was added 4.0 gms of Cabosil TS-610,dehydrated under vacuum above 100° C. To this slurry was added asolution of methylalumoxane (26 mls of 20 wt % MAO in toluene). Acatalyst precursor solution of 0.10 gms{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂ and 0.067 gms(n-C₃H₇-C₅H₄)(Me₅C)ZrCl₂ in about 20 mls toluene was added to theslurry, and stirred/swirled for about 30 minutes. This mixture was spraydried as above. The solids collected totaled 5.31 gms (60%). ICPindicated 0.37 wt % Zr and an Al:Zr ratio of 202:1.

[0167] Catalyst 9. Spray-Drying of 1:1{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂ and (n-C₃H₇-CsH₄)₂ZrCl₂

[0168] To 110 mls of toluene was added 4.0 gms of Cabosil TS-610,dehydrated under vacuum above 100° C. To this slurry was added asolution of methylalumoxane (26 mls of 20 wt % MAO in toluene). Acatalyst precursor solution of 0.10 gms{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBZ₂ and 0.056 gms (n-C₃H₇-C₅H₄)₂ZrCl₂ inabout 20 mls toluene was added to the slurry, and stirred/swirled forabout 30 minutes. This mixture was spray dried as above.

[0169] Catalyst 10. Spray-Drying of 3.4:1{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂ and (n-C₃H₇-C₅H₄)₂ZrCl₂

[0170] To 540 mls of toluene was added 21.4 gms of Cabosil TS-610,dehydrated under vacuum above 100° C. To this slurry was added asolution of methylalumoxane (97 mls of 20 wt % MAO in toluene). Acatalyst precursor solution of 0.80 gms{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂ and 0.143 gms (n-C₃H₇-C₅H₄)₂ZrCl₂ inabout 60 mls toluene was added to the slurry, and stirred/swirled forabout 30 minutes. This mixture was spray dried as above. The solidscollected totaled 21 gms (53%). ICP indicated 0.44 wt % Zr and an Al:Zrratio of 128.

[0171] Catalyst 11. Spray-Drying of 5:1{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂ and (n-C₃H₇-C₅H₄)₂ZrCl₂

[0172] To 570 mls of toluene was added 25.8 gms of Cabosil TS-610,dehydrated under vacuum above 100° C. To this slurry was added asolution of methylalumoxane (116 mls of 20 wt % MAO in toluene). Acatalyst precursor solution of 0.93 gms{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂ and 0.114 gms (n-C₃H₇-C₅H₄)₂ZrCl₂ inabout 40 mls toluene was added to the slurry, and stirred/swirled forabout 30 minutes. This mixture was spray dried as above. The solidscollected totaled 29 gms (60%). ICP indicated 0.39 wt % Zr and an Al:Zrratio of 156.

[0173] Catalyst 12. Spray-Drying of 3:1{[(2,4,6-Me₃C₆H₂)NCH₂CH₂₁₂NH}HfBz₂ and (n-C₃H₇-C₅H₄)₂ZrCl₂

[0174] To 570 mls of toluene was added 25.8 gms of Cabosil TS-610,dehydrated under vacuum above 100° C. To this slurry was added asolution of methylalumoxane (116 mls of 20 wt % MAO in toluene). Acatalyst precursor solution of 0.96 gms{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}HfBz₂ and 0.17 gms (n-C₃H₇-C₅H₄)₂ZrCl₂ inabout 40 mls toluene was added to the slurry, and stirred/swirled forabout 30 minutes. This mixture was spray dried as above. The solidscollected totaled 32 gms (67%). ICP indicated 0.51 wt % Hf, 0.094 wt %Zr and an Al:M ratio of 161.

Polymerization Examples 1-15

[0175] Polymerizations in a slurry reactor were conducted as follows.After an appropriate bake-out period and subsequent cool-down undernitrogen, 490 cc's of hexanes were charged to a 1 liter autoclavereactor. Hexene, if any, and 0.17 cc's of 0.87 mmolartriisobutylaluminum in heptane as scavenger, and hydrogen, if any, wereadded to the reactor prior to heating. The reactor contents were heatedto the desired temperature. Spray dried catalyst was loaded into a 10 ccbomb which was fitted to a 20 cc bomb to which was added 10 cc's ofhexanes. Each bomb was pressurized with nitrogen prior to attaching tothe reactor. The spray-dried catalyst was injected under pressure intothe reactor, followed immediately by release of the hexanes. In thismanner, quantitative delivery could be assured. Ethylene immediatelyfilled the system and was fed on demand thereafter. Polymerizations wereconducted for 30 minutes.

[0176] Comparative Polymerizations

[0177] The reactor was prepared and charged with hexane, hexene,hydrogen, and scavenger as above. The following preparation forComparative 1 is general: A stock solution of 2.1 mg of{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂ was dissolved in 4.5 cc's of toluene.A 0.50 cc aliquot was removed and added to 0.50 cc of 0.5 Mmethylaluminoxane (MAO) in toluene. The solutions were mixed for aboutfive minutes prior to injection into the reactor at the desired, afterwhich ethylene was immediately introduced and fed on demand thereafter.All polymerizations were conducted for 30 minutes.

[0178] The data are reported in the following table. rxn Cat- umolstorage Al/ temp cc cc C2 gms Mw x Ex. alyst M (days) Zr (° C.) H2 C6 PPPE activity¹ I₂₁ ² 10⁵ PDI³ 1 1 0.38 15 65 0 0 128 45.7 187900 2 1 0.3815 65 0 0 77 34.2 233800 3 1 0.50 33 65 0 20 60 27.9 186000 10.3 1.984.01 4 1 0.50 34 65 0 10 56 28.1 200700 2.36 3.07 5.55 5 1 0.38 55 65 00 62 23.8 202000 6 1 0.50 56 85 0 0 60 12.2  81300 051 7 2 2.3 65 0 0128 10.3  7000 8 2 3.0 65 0 20 129 12.4  6400 9 3 0.50 65 0 0 57 24.3170500 10 3 0.50 65 0 10 58 24.6 169700 1.67 3.14 4.51 11 3 0.50 85 0 055 18.4 133800 12 8 0.50 65 0 0 55 26.6 193400 nf 13 8 0.50 65 0 10 5721.9 153700 1.29 3.21 3.81 14 8 0.50 85 0 0 54 9.9  73300 nf 15 9 0.5065 100 0 65 8.7  53500 Comp 1 A 0.38 667 65 0 0 62 22.1 187600 Comp 2 A0.38 667 65 0 20 60 29.1 255300 Comp 3 B 3.0 500 65 0 0 135 3.2  1580Comp 4 B 3.0 500 65 0 20 135 3.2  1580

Polymerization Examples 16-21

[0179] After appropriate bake-out of a 4 L side-agitated laboratorygas-phase reactor and cool-down under nitrogen, the reactor was chargedwith Davison 955-600 silica as starting bed. Hydrogen, 1-hexene, andscavenger were added prior to heating to 85° C. Where added, hydrogenwas charged by filling a 50 cc bomb to 150 psig (1.03 MPa) with 5% H₂/N₂and discharging it to the reactor at slightly above ambient pressure.Spray-dried catalysts were injected into the reactor using the samedevice as was used for catalyst injection into the slurry reactor.Immediately upon catalyst injection, ethylene was introduced into thereactor and fed on demand for the remainder of the run. Ethylene partialpressure was 100 psig (0.69 MPa).

[0180] Comparative Polymerizations

[0181] Supported catalysts were run identically as above. Solutioncatalysts were injected in the same manner as for the slurrypolymerizations.

[0182] The data are reported in the following table. cata- ex- lyst/ am-pre- umol TIBA C6 silica PE time ple cursor M Al/M H₂ mls mls gms gmsmin 16 4 4.0 none 5 1.2 30 210 66 17 4 2.0 yes 4 0.6 30 141 94 18 5 4.0none 5 1.2 50 120 60 19 5 20 yes 4 0.6 30 107 75 20 7 2.0 yes 4 0.6 30148 60 21 8 2.0 yes 4 0.6 30 174 62 comp C 2.0 120 yes 4 0.6 30  31 60 5comp C 2.0 200 yes 4 0.6 30  56 132  6 comp C′ 2.0 120 yes 4 0.6 30  3862 7 comp D 2.0 200 yes 4 0.6 30  15 60 8

Polymerization Examples 22-28

[0183] Polymerization Procedure

[0184] In Comparative 9 and Examples 22 through 28, polyethylene wasprepared in a stirred bed, horizontally mixed reactor with variouscatalyst compositions. The Table below summarizes the polymerizationconditions for each example.

[0185]FIG. 1 depicts the horizontally mixed reactor system used inComparative 9 and Examples 22 through 28. The reactor was a two-phase(gas/solid) stirred bed, back-mixed reactor. A set of four “plows” 100were mounted horizontally on a central shaft rotating at 180 rpm to keepthe particles in reactor 110 mechanically fluidized. The reactorcylinder swept by these plows measured 40.6 cm (16 in.) long by 39.7 cm(15.6 in.) in diameter, resulting in a mechanically fluidizable volumeof 46 liters (1.6 ft³). The gas volume, larger than the mechanicallyfluidizable volume due to the vertical cylindrical chamber, totaled 54.6liters (1.93 ft³).

[0186] The reactor pressure in each example was 2.4 MPa. Ethylenemonomer, hexene comonomer and hydrogen (for molecular weight control)were fed to the reactor continuously via control valves through line120. The partial pressure of ethylene monomer was 1.5 Mpa. Comonomercontent in the polyethylene product was controlled by adjusting feedrates to maintain a constant comonomer/monomer molar ratio (shown in theTable) in the gas phase. Gas composition was measured at 1-4 minuteintervals by a gas chromatographic analyzer. Molecular weight of thepolyethylene was controlled by adjusting the hydrogen feed rate tomaintain a constant mole ratio of hydrogen to monomer in the gas phase.Nitrogen made up the majority of the balance of the composition of thegas in the reactor, entering with the catalyst composition through line130 and leaving via a small vent 140 with the reactor gases includingvolatilized solvents. The vent opening was adjusted via computer tomaintain constant total pressure in the reactor.

[0187] The reactor was cooled by an external jacket of chilled glycol.The bed temperature was measured with a temperature probe 150 in athermowell protruding into the bed at a 60° angle above horizontal,between the inner set of plows. The reactor temperature in Comparative 9was 85° C., while the reactor temperature in Examples 22 through 28 was80° C. For Comparative 9, a solution of catalyst was prepared by mixingCatalyst A in toluene and the resulting solution was stored in areservoir connected to line 160. The solution of catalyst was metered inshots via line 160 and mixed with a continuous stream of modifiedmethylaluminoxane cocatalyst solution introduced via line 170. Theconcentration of Akzo MMAO type 3A in isopentane was 2.1% and the amountof the MMAO used was such that the Al/Zr ratio in the reactor was 200.The mixture of catalyst and MMAO solutions were fed through a coil 180of ⅛ inch (0.32 cm) tubing where the catalyst and the cocatalyst reactedfor approximately 4 minutes. Upon leaving this pre-contact coil, themixed solution of catalyst composition was sprayed into the reactor by aconstant flow of nitrogen from line 130.

[0188] For Examples 22 through 28, a slurry of spray-dried catalyst wasprepared by mixing the catalyst powder with light mineral oil, and theresulting slurry was stored in an agitated reservoir connected to line160. The slurry of catalyst was metered in shots via line 160 and mixedwith a continuous stream of modified methylaluminoxane cocatalystsolution introduced via line 170. For these examples, coil 180 wasreplaced with a straight piece of ⅛″ o.d. tubing approximately 4″ long.The concentration of Akzo MMAO type 3A in isopentane was 2.1% and thefeedrate of MMAO solution was held fixed at approximately 50 ml/hr. Themixture of catalyst slurry and MMAO solution were fed to the reactor viaa ⅛ inch(0.32 cm) outer diameter injection tube using a constant flow ofnitrogen to disperse the mixture.

[0189] The reactor was run in both continuous and batch modes. Typicalbatch yields of granular polyethylene in the reactor were 7-20 lbs. Eachrun typically lasted 3-6 hours. In continuous mode, granular polymer waswithdrawn at 190 in typically 0.4 lb (0.2 kg) portions while thepolymerization was in progress. In the continuous mode, the productdischarge system was enabled after the bed weight built to 12-20 lbs(5.4-9.1 kg), and the rate of discharge was altered to maintain constantbed weight as calculated by material balance.

[0190] In each of Comparative 9 and Examples 22-28, the polymerizationprocess was begun by charging the monomers to the reactor and adjustingthe feeds until the desired gas composition was reached. An initialcharge of cocatalyst was added prior to starting catalyst feeding inorder to scavenge any poisons present in the reactor. After catalystfeed started, the monomers were added to the reactor in amountssufficient to maintain gas concentrations and ratios. As the catalystinventory built up, the polyethylene production rate increased to 5-10lbs/hr (2.3-4.5 kg/hr), at which point the catalyst feed was adjusted tomaintain a constant polyethylene production rate. For Comparative 9,cocatalyst feed rate was maintained in proportion to the catalyst feedrate. After the desired batch weight was made, the reactor was quicklyvented, and monomers were purged from the polyethylene resin withnitrogen. The batch was then discharged through valve 190 to the openatmosphere. temp H2/ C6/ yield yield MI FI density example catalyst (°C.) C2 C2 lbs kg dg/min dg/min g/cc comp 9 A 85 0.0015 0.0057 6.6 3.00.413 20.2 0.937 22  5 80 0.0013 0.0030 15.9 7.2 — 1.15 0.935 23 10 800.0013 0.0057 36.7 16.7 2.62 101.2 0.942 24 11 80 0.0013 0.0046 37.917.2 1.58 70.4 0.946 25 11 80 0.0012 0.0041 27.7 12.6 0.71 30.1 0.944 26 6 80 0.0020 0.0045 6.6 3.0 — 0.2 0.937 27 12 80 0.0019 0.0048 15.9 7.21.71 130.7 0.935 28 12 80 0.0008 0.0055 36.7 16.7 1.56 49.2 0.942

[0191] Indenyl zirconium tris pivalate when spray dried as describedherein produced polymer, but had low activity.

[0192] All documents described herein are incorporated by referenceherein, including any priority documents and/or testing procedures. Asis apparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly it is not intended thatthe invention be limited thereby.

1. A polymerization process comprising combining in the gas or slurryphase an olefin with a spray dried composition comprising an activator,a particulate filler and a metal catalyst compound comprising a Group 15metal compound and/or a phenoxide catalyst.
 2. The process of claim 1wherein the Group 15 metal compound is represented by the followingformulae:

wherein M is a group 3 to 14 metal, each X is independently an anionicleaving group, y is 0 or 1 (when y is 0 group L′ is absent) n is theoxidation state of M, m is the formal charge of the YZL ligand, Y is agroup 15 element, Z is a group 15 element, L′ is a Group 15 or 16element or Group 14 containing group, L is a group 15 or 16 element, R¹and R² are independently a C₁ to C₂₀ hydrocarbon group, a heteroatomcontaining group, silicon, germanium, tin, lead, phosphorus, or ahalogen, R¹ and R² may also be interconnected to each other, R³ isabsent, or is hydrogen, a group 14 atom containing group, a halogen, oraheteroatom containing group, R⁴ and R⁵ are independently an alkyl group,an aryl group, a substituted aryl group, a cyclic alkyl group, asubstituted cyclic alkyl group, or multiple ring system, R⁶ and R⁷ areindependently absent or hydrogen, an alkyl group, a halogen, aheteroatom or a hydrocarbyl group, or a heteroatom containing group, R*is absent, or is hydrogen, a Group 14 atom containing group, a halogen,or a heteroatom containing group.
 3. The process of claim 2 wherein M iszirconium or haffium.
 4. The process of claim 2 wherein each X isindependently hydrogen, halogen or a hydrocarbyl group
 5. The process ofclaim 2 wherein R¹ and R² are independently a C₁ to C₆ hydrocarbongroup.
 6. The process of claim 2 wherein R¹ and R² are a C₁ to C₂₀alkyl, aryl or aralkyl group.
 7. The process of claim 2 wherein m is 0,−1, −2, or −3 and n is +3, +4 or +5.
 8. The process of claim 2 whereinR³ is absent or hydrogen or methyl.
 9. The process of claim 2 wherein R⁴and R⁵ are independently a C₁ to C₂₀ hydrocarbon group.
 10. The processof claim 2 wherein R⁴ and R⁵ are independently a C₁ to C₂₀ aryl group ora C₁ to C₂₀ aralkyl group.
 11. The process of claim 2 wherein R⁴ and R⁵are independently a cyclic aralkyl group.
 12. The process of claim 2wherein R⁴ and R⁵ are independently a group represented by the followingformula:

wherein each R⁸ to R¹² are independently hydrogen, or a C₁ to C₂₀ alkylgroup, a heteroatom, or a heteroatom containing group having up to 40carbon atoms, and any two R groups can combine to form a cyclic group ora heterocyclic group.
 13. The process of claim 12 wherein R⁸ is methyl,ethyl, propyl or butyl and/or R⁹ is methyl, ethyl, propyl or butyl,and/or R¹⁰ is methyl, ethyl, propyl or butyl, and/or R¹¹ is methyl,ethyl, propyl or butyl and/or R¹² is methyl, ethyl, propyl or butyl. 14.The process of claim 13 wherein R⁹, R¹⁰ and R¹² are methyl and R⁸ and R¹are hydrogen.
 15. The process of claim 1 wherein the activator comprisesalkyl aluminum compounds, alumoxanes, modified alumoxanes,non-coordinating anions, boranes, borates and/or ionizing compounds. 16.The process of claim 1 wherein the olefin comprises ethylene.
 17. Theprocess of claim 1 wherein the olefin comprises propylene.
 18. Theprocess of claim 1 wherein the olefin comprises ethylene and a C₃ to C₂₀alpha olefin.
 19. The process of claim 1 , wherein the olefin comprisesethylene and hexene and/or butene.
 20. The process of claim 1 , whereinthe polymer produced has a molecular weight of 200,000 Daltons or more.21. The process of claim 1 wherein the filler is fumed silica treatedwith dimethylsilyldichloride.
 22. The process of claim 1 wherein thefiller comprises a finely divided polyolefin, talc, or an oxide ofsilica, magnesia, titania, alumina, or silica-alumina.
 23. The processof claim 1 wherein the transition metal compound and the activator arecombined, then mixed with filler, then spray dried, then placed in thegas or slurry phase.
 24. The process of claim 1 wherein a metal stearateis combined with the transition metal compound and/or the activatorand/or a filler.
 25. The process of claim 24 wherein the metal stearateis an aluminum stearate.
 26. The process of claim 25 wherein thealuminum stearate is aluminum distearate.
 27. The process of claim 1wherein the metal catalyst compound further comprises one or more bulkyligand metallocene-type compounds.
 28. The process of claim 1 whereinthe phenoxide catalyst is represented by the forumlae:

wherein R¹ is hydrogen or a C₄ to C₁₀₀ group and may or may not also bebound to M, and at least one of R² to R⁵ is a group containing a heteroatom, the rest of R² to R⁵ are independently hydrogen or a C₁ to C₁₀₀group, and any of R² to R⁵ also may or may not be bound to M, O isoxygen, M is a group 3 to group IO transition metal or lanthanide metal,Q is an alkyl, halogen, benzyl, amide, carboxylate, carbamate, thiolate,hydride or alkoxide group, or a bond to an R group containing aheteroatom which may be any of R¹ to R⁵, a heteroatom containing groupmay be any heteroatom or a heteroatom bound to carbon silica or anotherheteroatom, the heteroatom itself may be directly bound to the phenoxidering or it may be bound to another atom or atoms that are bound to thephenoxide ring, and any two adjacent R groups may form ring ormulti-ring structures.
 29. The process of claim 28 wherein R¹ is a C₄ toC₂₀ alkyl group or a C₄ to C₂₀ tertiary alkyl group or a neutral C₄ toC₁₀₀ group.
 30. The process of claim 28 wherein the rest of R² to R⁵ areindependently butyl, isobutyl, pentyl hexyl, heptyl, isohexyl, octyl,isooctyl, decyl, nonyl, or dodecyl.
 31. The process of claim 28 whereinM is Ti, Zr or Hf.
 32. The process of claim 28 wherein n is 3 or
 4. 33.The process of claim 28 wherein the heteroatom in the heteroatomcontaining group comprises boron, aluminum, silicon, nitrogen,phosphorus, arsenic, tin, lead, antimony, oxygen, selenium, sulfur,tellurium.
 34. The process of claim 28 wherein the heteroatom containinggroup comprises imines, amines, oxides, phosphines, ethers, ketenes,oxoazolines heterocyclics, oxazolines, and/or thioethers.
 35. Acomposition comprising particulate filler comprising fumed silicatreated with dimethylsilyldichloride and a metal catalyst compoundrepresented by the formulae:

wherein M is a group 3 to 14 metal, each X is independently an anionicleaving group, y is 0 or 1 (when y is 0 group L′ is absent) n is theoxidation state of M, m is the formal charge of the YZL ligand, Y is agroup 15 element, Z is a group 15 element, L′ is a Group 15 or 16element or Group 14 containing group, L is a group 15 or 16 element, R¹and R² are independently a C₁ to C₂₀ hydrocarbon group, a heteroatomcontaining group, silicon, germanium, tin, lead, phosphorus, or ahalogen, R¹ and R² may also be interconnected to each other, R³ isabsent, or is hydrogen, a group 14 atom containing group, a halogen, oraheteroatom containing group, R⁴ and R⁵ are independently an alkyl group,an aryl group, a substituted aryl group, a cyclic alkyl group, asubstituted cyclic alkyl group, or multiple ring system, R⁶ and R⁷ areindependently absent or hydrogen, an alkyl group, a halogen, aheteroatom or a hydrocarbyl group, or a heteroatom containing group, R*is absent, or is hydrogen, a Group 14 atom containing group, a halogen,or a heteroatom containing group.
 36. The composition of claim 35further comprising bulky ligand metallocene-type compound.
 37. Acomposition comprising particulate filler comprising fumed silicatreated with dimethylsilyldichloride and a metal catalyst compoundrepresented by the formula:

wherein R¹ is hydrogen or a C₄ to C₁₀₀ group and may or may not also bebound to M, and at least one of R² to R¹ is a group containing aheteroatom, the rest of R² to R⁵ are independently hydrogen or a C₁ toC₁₀₀ group, and any of R² to R⁵ also may or may not be bound to M, O isoxygen, M is a group 3 to group 10 transition metal or lanthanide metal,Q is an alkyl, halogen, benzyl, amide, carboxylate, carbamate, thiolate,hydride or alkoxide group, or a bond to an R group containing aheteroatom which may be any of R¹ to R⁵, a heteroatom containing groupmay be any heteroatom or a heteroatom bound to carbon silica or anotherheteroatom, the heteroatom itself may be directly bound to the phenoxidering or it may be bound to another atom or atoms that are bound to thephenoxide ring, ands any two adjacent R groups may form ring ormulit-ring structures.
 38. The composition of claim 37 furthercomprising bulky ligand metallocene-type compound.
 39. The compositionof claim 35 further comprising a metal catalyst compound represented bythe formula:

wherein R¹ is hydrogen or a C₄ to C₁₀₀ group and may or may not also bebound to M, and at least one of R² to R⁵ is a group containing aheteroatom, the rest of R² to R⁵ are independently hydrogen or a C₁ toC₁₀₀ group, and any of R² to R⁵ also may or may not be bound to M, O isoxygen, M is a group 3 to group 10 transition metal or lanthanide metal,Q is an alkyl, halogen, benzyl, amide, carboxylate, carbamate, thiolate,hydride or alkoxide group, or a bond to an R group containing aheteroatom which may be any of R¹ to R⁵, a heteroatom containing groupmay be any heteroatom or a heteroatom bound to carbon silica or anotherheteroatom, the heteroatom itself may be directly bound to the phenoxidering or it may be bound to another atom or atoms that are bound to thephenoxide ring, ands any two adjacent R groups may form ring ormulit-ring structures.
 40. The composition of claim 39 furthercomprising a bulky ligand metallocene-type compound.